JP5588640B2 - Laminated sheet for automotive interior materials - Google Patents

Description

  The present invention relates to a laminated sheet for automobile interior materials used for automobile interior materials such as automobile ceiling materials and door members.

  Conventionally, various automobile interior materials have been proposed. As an automotive interior material, for example, Patent Document 1 discloses an automotive ceiling material in which a modified polyphenylene ether-based resin non-foamed layer is formed on the upper surface and / or the lower surface of a modified polyphenylene ether-based resin foam layer. An automotive ceiling material has been proposed in which the glass transition temperature of the ether-based resin non-foamed layer is lower than the glass transition temperature of the modified polyphenylene ether-based resin foamed layer.

  On the other hand, an increase in average temperature has become a global problem due to the recent global warming. In particular, in summer, the temperature is often high, which was rarely found in the past. For this reason, if an automobile is left outdoors in the summer, the temperature inside the vehicle becomes high, causing problems such as deformation of the interior material in a high temperature atmosphere or drooping due to its own weight.

  Therefore, there is a demand for an automobile interior material that does not deform even in the interior of an automobile that becomes hot in summer. Since the ceiling material for automobiles depends on the non-foamed layer for its heat resistance, it can be dealt with by increasing the glass transition temperature of the modified polyphenylene ether resin constituting the non-foamed layer.

  However, in the above-mentioned automotive ceiling material, if the glass transition temperature of the modified polyphenylene ether resin constituting the non-foamed layer is increased, the glass transition temperature of the modified polyphenylene ether resin constituting the foamed layer must also be increased. There is.

  On the other hand, the ceiling material for automobiles is attached to the automobile after being formed into a desired shape by thermoforming. Moreover, the foam layer of the ceiling material for automobiles itself is a heat insulating layer.

  Therefore, if the glass transition temperature of the modified polyphenylene ether resin constituting the foam layer is increased, the amount of heat for heating the foam layer as a whole is further required, and the interior of the foam layer is sufficiently heated. As a result, the heating of the foam layer is insufficient, the moldability of the foam layer is reduced, and the surface of the ceiling material for automobiles is flawed and the moldability of the ceiling material for automobiles is reduced. Problems arise.

  In addition, since the foam layer has the above-mentioned heat insulating action, there is a limit to increasing the glass transition temperature of the modified polyphenylene ether resin constituting the foam layer in consideration of heating of the foam layer during thermoforming. Therefore, there is a limit to increasing the glass transition temperature of the modified polyphenylene ether resin constituting the non-foamed layer.

  Furthermore, after the thermoforming of the automotive ceiling material, it is necessary to cool the automotive ceiling material, but due to the configuration in which the foamed layer has higher heat resistance than the non-foamed layer, the foamed layer is heated to a higher temperature during thermoforming. Since it is necessary to heat and the foam layer itself has a heat insulating property, it takes time to cool the foam layer of the automobile ceiling material after it is taken out from the mold, and the time required for molding (molding time) ) Becomes longer.

Japanese Patent No. 3792746

  The present invention provides a laminated sheet for automobile interior materials that has excellent heat resistance and moldability and can shorten the molding cycle.

  Modified polyphenylene ether-based resin foam sheet (hereinafter sometimes abbreviated as “foamed sheet”) and modified polyphenylene ether-based resin non-foamed sheet (hereinafter referred to as “non-foamed sheet”) of the laminated sheet for automobile interior materials of the present invention. There is no particular limitation on the modified polyphenylene ether-based resin constituting the mixture, and a mixture of a polyphenylene ether and a polystyrene-based resin represented by the following chemical formula 1 is graft copolymerized with a styrene monomer on the polyphenylene ether. The modified polyphenylene ether, a mixture of the modified polyphenylene ether and polystyrene resin, and the phenolic monomer and styrene monomer represented by the following chemical formula 2 are oxidatively polymerized in the presence of a catalyst such as an amine complex of copper (II). Block copolymer obtained by this, this block copolymer And a mixture of the body and polystyrene resin. The modified polyphenylene ether resin may be used alone or in combination.

（Ｒ₁ 、Ｒ₂ は炭素数が１〜４のアルキル基又はハロゲン原子を示し、ｎは重合度を示す。）

(R ₁ and R ₂ represent an alkyl group having 1 to 4 carbon atoms or a halogen atom, and n represents the degree of polymerization.)

  Examples of the polyphenylene ether represented by the above chemical formula 1 include poly (2,6-dimethylphenylene-1,4-ether), poly (2,6-diethylphenylene-1,4-ether), poly (2, 6-dichlorophenylene-1,4-ether), poly (2,6-dibromophenylene-1,4-ether), poly (2-methyl-6-ethylphenylene-1,4-ether), poly (2- Chloro-6-methylphenylene-1,4-ether), poly (2-methyl-6-isopropylphenylene-1,4-ether), poly (2,6-di-n-propylphenylene-1,4-ether) ), Poly (2-bromo-6-methylphenylene-1,4-ether), poly (2-chloro-6-bromophenylene-1,4-ether), poly (2-chloro-6-ether) Rufeniren 1,4 ether). The polyphenylene ether represented by Chemical Formula 1 may be used alone or in combination, and those having a polymerization degree n of 10 to 5000 are usually used.

（Ｒ₃ 、Ｒ₄ は炭素数が１〜４のアルキル基又はハロゲン原子を示す。）

(R ₃ and R ₄ represent an alkyl group having 1 to 4 carbon atoms or a halogen atom.)

  Examples of the phenolic monomer represented by the above chemical formula 2 include 2,6-dimethylphenol, 2,6-diethylpheninol, 2,6-dichlorophenol, 2,6-dibromophenol, 2-methyl-6- Ethylphenol, 2-chloro-6-methylphenol, 2-methyl-6-isopropylphenol, 2,6-di-n-propylphenol, 2-bromo-6-methylphenol, 2-chloro-6-bromophenol, Examples include 2-chloro-6-ethylphenol. The phenolic monomer represented by Chemical Formula 2 may be used alone or in combination.

  Examples of the polystyrene resin mixed with the polyphenylene ether, the modified polyphenylene ether, or the block copolymer include polystyrene, a copolymer of styrene and a vinyl monomer copolymerizable therewith, and high impact polystyrene. And polystyrene is preferred. Polystyrene resins may be used alone or in combination.

  Examples of the vinyl monomer include methyl methacrylate, acrylonitrile, methacrylonitrile, and butyl acrylate. Moreover, as high impact polystyrene, rubber components such as styrene-butadiene copolymer and styrene-butadiene-styrene block copolymer are added to polystyrene or a copolymer of styrene and a vinyl monomer copolymerizable therewith. The thing formed by adding 1 to 20 weight% is mentioned.

  Examples of the styrene monomer that is graft copolymerized with polyphenylene ether or block copolymerized with a phenol monomer include styrene, alkylated styrene, and halogenated styrene.

  Examples of the alkylated styrene include α-methyl styrene, 2,4-dimethyl styrene, p-methyl styrene, ethyl styrene, pt-butyl styrene, and the like. Examples of the halogenated styrene include monochlorostyrene and dichlorostyrene.

  When the expansion ratio of the foamed sheet constituting the laminated sheet for automobile interior material of the present invention is small, the heat insulating property of the obtained laminated sheet for automobile interior material may be lowered. Since the mechanical strength and formability of the laminated sheet for materials may be lowered, 5 to 30 times is preferable, and 7 to 25 times is more preferable. The expansion ratio of the foamed sheet refers to a value obtained by dividing the average specific gravity of the synthetic resin constituting the foamed sheet by the specific gravity of the foamed sheet.

  In addition, if the thickness of the foam sheet is thin, the thickness of the molded product obtained by molding the resulting laminated sheet for automobile interior materials is reduced, and the mechanical strength and heat insulation of the molded product may be reduced, If it is thick, the formability of the resulting laminated sheet for automobile interior materials may be reduced, so 2 to 10 mm is preferable, and 2 to 8 mm is more preferable.

Open cell ratio of the modified polyphenylene ether-based resin foam sheet, when requesting the sound absorption properties to denatured polyphenylene ether-based resin foam sheet is limited to 50-90%.

  In addition, the open cell rate of the modified polyphenylene ether-based resin foam sheet refers to that measured by a 1-1 / 2 atm method in accordance with ASTM D-2856-87. Specifically, a plurality of planar square sheet-like test pieces each having a side of 25 mm are cut out from the modified polyphenylene ether-based resin foam sheet over the entire length in the thickness direction of the foam sheet. The laminated body is formed by superposing the whole thickness in the thickness direction so as to be about 25 mm.

Next, after accurately measuring the apparent volume of the laminate using a caliper, the volume of the laminate is measured by the 1-1 / 2-1 atmospheric pressure method using an air-comparing hydrometer, and continuously according to the following formula. Measure the bubble rate. In addition, the volume of the laminated body by the 1-1 / 2-1 atmospheric pressure method is measured using the air comparison type hydrometer which is marketed with the brand name "air comparison type hydrometer 1000 type | mold" from Tokyo Science, for example. be able to.
Open cell ratio (%) = 100 × (apparent volume−volume of laminate by air comparison type hydrometer)
/ Apparent volume

  For foamed sheets, inorganic fillers such as talc, fatty acid metal salts such as stearic acid metal salts, flame retardants, lubricants, and improved impact resistance, as long as the physical properties of the foamed sheets are not impaired. Agents, pigments, stabilizers and the like may be added.

  The laminated sheet for automobile interior material of the present invention is formed by laminating and integrating a non-foamed sheet on both surfaces of the foamed sheet. In addition, it is preferable that the non-foamed sheet is directly heat-sealed and integrated without interposing an adhesive on both surfaces of the foamed sheet. Further, the modified polyphenylene ether resins constituting the non-foamed sheet laminated and integrated on both surfaces of the foamed sheet may be the same or different, but are preferably the same.

  The glass transition temperature of the modified polyphenylene ether resin constituting the non-foamed sheet is configured to be higher than the glass transition temperature of the modified polyphenylene ether resin constituting the foamed sheet. The sheet is configured to have better heat resistance than the foam sheet.

  The glass transition temperature of the modified polyphenylene ether-based resin refers to a temperature measured under a temperature raising / lowering rate of 20 ° C./min in accordance with JIS K7121. The glass transition temperature of the modified polyphenylene ether resin can be measured, for example, using a trade name “DSC6220 type” from SII Technology.

  As a standard for adjusting the glass transition temperature of the modified polyphenylene ether resin, a phenylene ether component in the modified polyphenylene ether resin can be mentioned. When the amount of the phenylene ether component in the modified polyphenylene ether resin is reduced, the glass transition temperature of the modified polyphenylene ether resin tends to be lowered. When the amount of the phenylene ether component in the modified polyphenylene ether resin is increased, the glass transition temperature of the modified polyphenylene ether resin tends to increase.

  Then, the amount of the phenylene ether component in the modified polyphenylene ether resin constituting the non-foamed sheet is adjusted to be larger than the amount of the phenylene ether component in the modified polyphenylene ether resin constituting the foamed sheet. Thus, the glass transition temperature of the modified polyphenylene ether resin constituting the non-foamed sheet can be adjusted to be higher than the glass transition temperature of the modified polyphenylene ether resin constituting the foamed sheet.

  When the polystyrene resin is mixed with the polyphenylene ether resin, the content of the phenylene ether component is the content after including the polystyrene resin.

  In the laminated sheet for automobile interior materials according to the present invention, the non-foamed sheet is not foamed and there are no bubbles due to foaming, so it is easily heated to a desired temperature by heating. On the other hand, the foam sheet has air bubbles inside and has heat insulation properties. Accordingly, when heating the foam sheet, a large amount of heat is required to sufficiently heat the inside of the foam sheet.

  The laminated sheet for automobile interior material of the present invention is used by being attached to an automobile after being formed into a desired shape by thermoforming to be an automobile interior material. In the heating at the time of thermoforming the laminated sheet for automobile interior materials, the non-foamed sheet can be easily heated to a desired temperature as described above. Furthermore, since the heat resistance of the foam sheet is lower than that of the non-foamed sheet, the foam sheet is generally fully at the temperature required for thermoforming at the temperature at which the non-foamed sheet is heated for thermoforming. Heated. Therefore, the laminated sheet for automobile interior materials can be heated in a short time to the softened state necessary for thermoforming with as little heat as possible, thereby shortening the molding time and saving energy.

  And although the laminated sheet for automotive interior materials is thermoformed and formed into the automotive interior material, it is cooled, but as described above, the laminated sheet for automotive interior materials is not excessively heated during thermoforming. Since the non-foamed sheet is easy to heat as described above, it can be easily cooled. Furthermore, although the foam sheet itself has a heat insulating property, as described above, since it is heated with a small amount of heat, the foam sheet retains a small amount of heat, and the foam sheet can be easily cooled. It can be carried out. Therefore, the automobile interior material obtained by thermoforming the laminated sheet for automobile interior material can be cooled in a short time after being taken out of the mold, and the molding time of the laminated sheet for automobile interior material is shortened. Can be achieved.

  Further, in the laminated sheet for automobile interior material, the heat resistance of the foam sheet is lowered to improve the moldability of the laminated sheet for automobile interior material as described above. In addition, the non-foamed sheet is superior to the non-foamed sheet, and the thickness of the non-foamed sheet is larger than the thickness of the cell wall of the foamed sheet.

  Therefore, even when the automobile interior material obtained by thermoforming the laminated sheet for automobile interior material is left in a high temperature atmosphere and the foamed sheet of the laminated sheet for automobile interior material becomes soft, the non-foamed sheet is deformed. Therefore, the vehicle interior material as a whole is not deformed or hangs down due to its own weight.

  If the amount of the phenylene ether component in the modified polyphenylene ether resin constituting the foamed sheet is small, the heat resistance of the laminated sheet for automobile interior materials may be reduced. Since the property may be lowered, the content is preferably 25 to 50% by weight, more preferably 30 to 45% by weight.

  In addition, if the amount of the phenylene ether component in the modified polyphenylene ether resin constituting the non-foamed sheet is small, the heat resistance of the laminated sheet for automobile interior material may be lowered. Since the formability of the sheet may deteriorate, it is preferably 26 to 51% by weight, and more preferably 31 to 36% by weight.

The difference between the glass transition temperature of the modified polyphenylene ether resin constituting the non-foamed sheet and the glass transition temperature of the modified polyphenylene ether resin constituting the foamed sheet is limited to 1 to 7 ° C. , but 2 ~5 ℃ is good Masui. This is because if the temperature difference is small, the heat resistance of the laminated sheet for automobile interior materials may be lowered. This is because if the temperature difference is large, the moldability of the laminated sheet for automobile interior materials may be lowered.

  A non-foamed sheet may contain a colorant. The colorant is not particularly limited, and examples thereof include inorganic fillers such as carbon black, titanium oxide, zinc oxide, iron oxide, and aluminum oxide, cyanine blue, cyanine green, miloli blue, slen blue, cadmium red, cadmium yellow, and cadmium. Examples thereof include pigments such as orange, petal, ultramarine blue, and phthalocyanine blue. Colorants exhibiting dark colors such as black and gray are preferable, and carbon black is more preferable.

  Furthermore, a rubber component may be added to the non-foamed sheet in order to prevent embrittlement. Examples of the rubber component include high impact polystyrene, styrene-butadiene copolymer, styrene-butadiene-styrene block copolymer, and high impact polystyrene is preferable.

  If the content of the rubber component in the non-foamed sheet of the modified polyphenylene ether resin is small, the effect of preventing embrittlement of the non-foamed sheet may not be exhibited, and if it is large, the bending strength and rigidity of the non-foamed sheet are lowered. Therefore, 1 to 20 parts by weight is preferable with respect to 100 parts by weight of the modified polyphenylene ether resin.

  If the thickness of the non-foamed sheet is thin, the mechanical strength of the laminated sheet for automotive interior materials may be reduced, and if thick, the moldability and lightness of the laminated sheet for automotive interior materials may be reduced. 50-300 micrometers is preferable and 70-200 micrometers is more preferable.

  Next, the manufacturing method of the laminated sheet for automobile interior materials will be described. First, as a method for producing a foam sheet, specifically, for example, (1) a modified polyphenylene ether resin is supplied to an extruder and melt-kneaded, and a volatile foaming agent is press-fitted into the extruder, and then the extruder (2) A modified polyphenylene ether resin is impregnated with a volatile foaming agent in advance and then supplied to the extruder, melt-kneaded, and attached to the extruder. Examples thereof include a method for producing a foam sheet that is extruded and foamed from a mold.

  The volatile blowing agent is not particularly limited as long as it is conventionally used. For example, organic blowing agents such as ethane, propane, isobutane, normal butane, pentane, and dimethyl ether, carbon dioxide, water, An inorganic foaming agent such as nitrogen is used. A volatile foaming agent may be used independently or 2 or more types may be used together.

  And as a method of laminating and integrating a non-foamed sheet on both sides of the foamed sheet 1 obtained as described above, for example, (1) a non-foamed sheet is laminated on both sides of the foamed sheet, and the foamed sheet is heated by a hot roll. (2) A non-foamed sheet immediately after being extruded from an extruder is laminated on both sides of the foamed sheet, and this sheet is heat-sealed on both sides of the foamed sheet. And (3) a method in which non-foamed sheets are laminated and integrated on both surfaces of a foamed sheet by coextrusion.

  In addition, a laminated sheet for automobile interior materials is usually laminated and integrated on one surface with a skin material disposed on the inside of the vehicle via an adhesive layer, and an abnormal sound preventing layer is laminated and integrated on the other surface. It is thermoformed into a desired shape by thermoforming and used as an automobile interior material.

  Examples of the skin material include non-woven fabric, woven fabric, and knitted fabric, and preferably have air permeability. Note that a flame retardant may be included in order to impart flame retardancy to the skin material.

  The fibers constituting the skin material include polyesters such as polyethylene terephthalate, synthetic fibers such as polyamide and polyacrylonitrile, polyester fibers are preferable, and polyethylene terephthalate fibers are more preferable in terms of excellent heat resistance. . In addition, the fibers constituting the skin material may be used alone or in combination.

  The adhesive layer is not particularly limited as long as the skin material and the laminated sheet for automobile interior materials can be bonded and integrated. For example, a thermoplastic adhesive, a hot-melt adhesive, a rubber adhesive, a heat Examples thereof include curable adhesives, monomer-reactive adhesives, inorganic adhesives, natural material-based adhesives, etc. Hot melt adhesives are preferred because they can be easily bonded.

  Examples of the hot melt adhesive include polyolefin resins, modified polyolefin resins, polyurethane resins, ethylene-vinyl acetate copolymer resins, polyamide resins, polyester resins, thermoplastic elastomer resins, styrene- Examples thereof include butadiene copolymer resin and styrene-isoprene copolymer resin as components. A hot-melt-adhesive may be used independently or 2 or more types may be used together.

  Further, as described above, the noise prevention layer may be laminated and integrated on the other surface of the laminated sheet for automobile interior materials. The noise prevention layer is for reducing the friction noise generated when the laminated sheet for automobile interior materials is in sliding contact with the steel sheet constituting the car body of the automobile. A polyolefin resin film or a nonwoven fabric is preferably used, and the nonwoven fabric is used. Is more preferably used.

  Examples of the polyolefin resin film include polyolefin resin films such as polyethylene film and polypropylene film, which are excellent in heat resistance and stably generate frictional noise over a long period of time regardless of ambient temperature changes. An unstretched polypropylene film is preferable in that it can be reduced. In addition, 10-100 micrometers is preferable and, as for the thickness of the said polyolefin resin film, 25-35 micrometers is more preferable.

  Furthermore, it does not specifically limit as a fiber which comprises the nonwoven fabric used for a noise prevention layer, For example, synthetic resin fibers, such as a polyester fiber, a polyethylene fiber, a polypropylene fiber, a polyamide fiber, a polyacrylonitrile fiber, etc. are mentioned.

  Next, as described above, the laminated sheet for automobile interior materials is formed in a desired shape by thermoforming, with a skin material laminated and integrated on one side and a noise prevention layer laminated on the other side as necessary. It is formed into a car interior material.

  As a method for thermoforming the laminated sheet for automobile interior material, a general-purpose method has been conventionally used. For example, after the laminated sheet for automobile interior material is heated and secondarily foamed, the second foamed automobile is used. The laminated sheet for interior material may be thermoformed using a general-purpose forming method such as vacuum forming or pressure forming.

  As vacuum forming and pressure forming, for example, plug forming, free drawing forming, plug and ridge forming, matched mold forming, straight forming, drape forming, reverse draw forming, air slip forming, plug assist forming, plug Examples include assist reverse draw molding. In the molding method, it is preferable to use a mold whose temperature can be adjusted.

  As described above, the laminated sheet for automobile interior material according to the present invention comprises a modified polyphenylene ether resin non-foamed sheet that is lower than the glass transition temperature of the modified polyphenylene ether resin that constitutes the modified polyphenylene ether resin foam sheet. The modified polyphenylene ether-based resin is configured to have a higher glass transition temperature.

  Therefore, when thermoforming a laminated sheet for automobile interior materials, the modified polyphenylene ether resin non-foamed sheet is heated to a temperature necessary for thermoforming, so that the modified polyphenylene ether resin foam sheet is also required for thermoforming to the inside. The entire laminated sheet for automobile interior materials can be heated to a temperature required for thermoforming with as little heat as possible and accurately formed into a desired shape.

  And, since the heating of the modified polyphenylene ether-based resin foam sheet is suppressed as much as possible at the time of cooling after the thermoforming of the laminated sheet for automobile interior materials, the modified polyphenylene ether-based resin foam sheet has a heat insulating effect. Nevertheless, the cooling of the modified polyphenylene ether-based resin foam sheet can be completed in a short time, and the molding time of the laminated sheet for automobile interior materials can be shortened.

  In the laminated sheet for automobile interior material of the present invention, the heat resistance of the modified polyphenylene ether resin non-foamed sheet is improved more than the heat resistance of the modified polyphenylene ether resin foam sheet. Even when the automotive interior material obtained by thermoforming is used at a high temperature, the non-foamed sheet maintains its shape, and the laminated sheet for automotive interior material or the automotive interior material is heated during use. The shape is not deformed by the above, and the shape is reliably maintained.

  Next, examples of the present invention will be described, but the present invention is not limited to the following examples.

(Examples 1-3 , Comparative Examples 1-5 )
A tandem type first extruder having a second stage extruder connected to the tip of the first stage extruder was prepared. Mixture of polyphenylene ether resin and polystyrene resin (trade name “NORYL PKN4752” manufactured by SABIC Innovative Plastics Japan Co., Ltd., phenylene ether component: 70% by weight, styrene component: 30% by weight) and polystyrene (manufactured by Toyo Styrene Co., Ltd.) Named “HRM-26”) and 100 parts by weight of a modified polyphenylene ether resin and 0.7 parts by weight of talc mixed with the phenylene ether component and the styrene component adjusted so as to have the contents shown in Table 1. Was fed to the first stage extruder and melt kneaded.

Further, a volatile foaming agent consisting of 35% by weight of isobutane and 65% by weight of normal butane was press-fitted into the first stage extruder so as to be 4.5 parts by weight with respect to 100 parts by weight of the modified polyphenylene ether resin. And kneaded. Thereafter, the molten modified polyphenylene ether resin is continuously supplied to the second stage extruder, and is extruded and foamed into a cylindrical shape from a circular mold attached to the tip of the second stage extruder. A cylindrical foam is manufactured, and the cylindrical foam is gradually expanded in diameter, supplied to a mandrel, cooled, and then the cylindrical foam is extruded between the inner and outer peripheral surfaces at arbitrary locations. By continuously cutting and developing in the direction, a long modified polyphenylene ether-based resin foam sheet was obtained. The obtained foam sheet had a basis weight of 250 g / m ² , a thickness of 5.1 mm, an expansion ratio of 21.4 times, and an open cell ratio of 80%. The glass transition temperature of the modified polyphenylene ether resin constituting the modified polyphenylene ether resin foamed sheet was as shown in Table 1.

  Two second extruders were prepared. Mixture of polyphenylene ether resin and polystyrene resin (trade name “NORYL PKN4752” manufactured by SABIC Innovative Plastics Japan Co., Ltd., phenylene ether component: 70% by weight, styrene component: 30% by weight) and polystyrene (manufactured by Toyo Styrene Co., Ltd.) Name “HRM-26”) and high impact polystyrene (trade name “E641N” manufactured by Toyo Styrene Co., Ltd.) are mixed while adjusting the phenylene ether component, styrene component and rubber component to the contents shown in Table 1. The modified polyphenylene ether resin thus prepared was supplied to each of the second extruders, melted and kneaded, and a modified polyphenylene ether resin non-foamed sheet was extruded from each second extruder.

  Next, one side of the modified polyphenylene ether resin foam sheet obtained by extrusion foaming from the second stage extruder of the first extruder, the molten modified polyphenylene ether system extruded from one second extruder Resin non-foamed sheets were laminated and integrated by heat fusion. At the same time, the modified polyphenylene ether in the molten state extruded from the other second extruder is also applied to the other surface of the modified polyphenylene ether-based resin foam sheet obtained by extrusion foaming from the second stage extruder of the first extruder. A laminated sheet for automobile interior material was obtained by laminating a non-foamed resin sheet and integrating it by heat fusion.

In the obtained laminated sheet for automobile interior materials, the modified polyphenylene ether-based resin non-foamed sheet was laminated and integrated directly on both sides of the modified polyphenylene ether-based resin foamed sheet by thermal fusion. The modified polyphenylene ether resin non-foamed sheet had a basis weight of 100 g / m ² and a thickness of 95 μm. Table 1 shows the glass transition temperature of the modified polyphenylene ether resin constituting the non-foamed sheet of the modified polyphenylene ether resin.

On one side of the obtained laminated sheet for automobile interior materials, a hot melt film (trade name “X-2200” manufactured by Kurabo Industries, thickness: 30 μm, melting point: 92 ° C.) mainly composed of an ethylene-ethyl acrylate copolymer. The skin material (weight per unit area: 130 g / m ² ) was superposed so that the hot melt film was on the laminated sheet side for automobile interior materials.

Further, on the other surface of the obtained laminated sheet for automobile interior materials, a spunbonded nonwoven fabric (trade name “Ecule 615 AD” manufactured by Toyobo Co., Ltd., weight per unit: 20 g / m) made of polyester fiber with hot-melt powder serving as an anti-noise layer. A polymerization sheet was produced by superimposing m ² ).

  A roller press provided with a pair of polytetrafluoroethylene belts was prepared. The temperature of the roller press machine belt was maintained at 115-135 ° C. A polymerization sheet is supplied between the belts of the roller press machine and the polymerization sheet is compressed in the thickness direction from both sides, and the skin material is laminated and integrated on one surface of the laminated sheet for automobile interior material. An anti-noise layer was laminated and integrated on the other side.

  About the obtained laminated sheet for automobile interior materials, heat resistance, molding time and moldability were measured in the following manner, and the results are shown in Table 1. In Table 1, the difference in glass transition temperature is the modified polyphenylene ether constituting the modified polyphenylene ether resin foam sheet from the glass transition temperature of the modified polyphenylene ether resin constituting the modified polyphenylene ether resin non-foamed sheet. The value obtained by subtracting the glass transition temperature of the resin was shown.

(Heat-resistant)
A laminated sheet for automobile interior material was molded by hot press molding to obtain a tray-shaped molded product. The obtained molded product has a flat rectangular bottom surface portion, a peripheral wall portion extending upward from the outer peripheral edge of the bottom surface portion, and a flange portion extending outward from the outer peripheral edge of the peripheral wall portion. Was composed. The molded product immediately after molding was placed on a horizontal surface in a state where the bottom surface portion was in contact with the horizontal surface. In this state, the vertical distance between the outer peripheral edge of the flange and the horizontal plane passing through the upper end of the peripheral wall was measured, and this distance was defined as H ₁ (mm).

Next, after allowing the molded product to stand in an oven maintained at 100 ° C. for 24 hours, the molded product was taken out of the oven, and the molded product was cooled until its surface temperature reached room temperature. Thereafter, the molded product was placed on a horizontal surface in a state where the bottom surface portion was in contact with the horizontal surface. In this state, the vertical distance between the outer peripheral edge of the flange and the horizontal plane passing through the upper end of the peripheral wall was measured, and this distance was defined as H ₂ (mm).

And deformation amount (DELTA) H was computed based on the following formula, and it evaluated based on the following reference | standard. In addition, ΔH is described in parentheses in Table 1.
ΔH (mm) = H ₂ −H ₁

A: Deformation amount ΔH was 2 mm or less.
B: Deformation amount ΔH was more than 2 mm and 4 mm or less.
C: Deformation amount ΔH exceeded 4 mm.

(Molding time and formability)
A general-purpose single-shot molding machine was prepared. After the upper heater temperature of the molding machine is set to 250 ° C. and the lower heater temperature is set to 230 ° C., the laminated sheet for automobile interior material is supplied between the male and female molds of the molding machine and laminated for automobile interior material for 30 seconds. The sheet was heated.

  Next, the male and female molds of the molding machine were clamped, and the laminated sheet for automobile interior material was thermoformed into a tray shape for 30 seconds. The clearance between the male and female dies was 4 mm. Thereafter, the laminated sheet for automobile interior material was cooled by cooling the male and female molds until the surface temperature reached 60 ° C., and then the male and male molds were opened to take out a tray-shaped molded product.

  Measure the time required to supply the laminated sheet for automobile interior materials between the male and female molds of the molding machine until the male and female molds are opened and take out the tray-shaped molded product. . The measured molding times are shown in Table 1. Further, the obtained molded product was visually observed and the moldability was evaluated based on the following criteria.

A: There were no creases, wrinkles or cracks on the surface of the molded product.
B: Although there were no creases and cracks on the surface of the molded product, wrinkles were generated.
C: A crease or a crack occurred on the surface of the molded product.

Claims (1)

Modified polyphenylene ether resin foam sheet having an open cell ratio of 50 to 90%, and modified polyphenylene ether resin laminated and integrated on both surfaces of the modified polyphenylene ether resin and constituting the modified polyphenylene ether resin foam sheet a modified polyphenylene ether-based resin non-foamed sheet and a modified polyphenylene ether resin having a high glass transition temperature than the glass transition temperature of the resin or a laminated sheet for including automotive interior materials,
The content of the phenylene ether component of the modified polyphenylene ether resin constituting the non-foamed sheet of the modified polyphenylene ether resin is phenylene of the modified polyphenylene ether resin constituting the foamed sheet of the modified polyphenylene ether resin. Higher than the content of the ether component, and
The glass transition temperature of the modified polyphenylene ether resin constituting the modified polyphenylene ether resin non-foamed sheet and the glass transition temperature of the modified polyphenylene ether resin constituting the modified polyphenylene ether resin foam sheet. The laminated sheet for automotive interior materials , wherein the difference is 1 to 7 ° C.